Results for “templated assembly” — Page 6

DOE OSTI2024

A single diiron enzyme catalyses the oxidative rearrangement of tryptophan to indole nitrile

Abstract Nitriles are uncommon in nature and are typically constructed from oximes through the oxidative decarboxylation of amino acid substrates or from the derivatization of carboxylic acids. Here we report a third nitrile biosynthesis strategy featuring the cyanobacterial nitrile synthase AetD. During the biosynthesis of the eagle-killing neurotoxin, aetokthonotoxin, AetD transforms the 2-aminopropionate portion of 5,7-dibromo-l-tryptophan to a nitrile. Employing a combination of structural, biochemical and biophysical techniques, we characterized AetD as a non-haem diiron enzyme that belongs to the emerging haem-oxygenase-like dimetal oxidase superfamily. High-resolution crystal structures of AetD together with the identification of catalytically relevant products provide mechanistic insights into how AetD affords this unique transformation, which we propose proceeds via an aziridine intermediate. Our work presents a unique template for nitrile biogenesis and portrays a substrate binding and metallocofactor assembly mechanism that may be shared among other haem-oxygenase-like dimetal oxidase enzymes.

Chemistry↗

DOE OSTI2022

Metastable doubly threaded [3]rotaxanes with a large macrocycle

Ring size is a critically important parameter in many interlocked molecules as it directly impacts many of the unique molecular motions that they exhibit. Reported herein are studies using one of the largest macrocycles reported to date to synthesize doubly threaded [3]rotaxanes. A large ditopic 46 atom macrocycle containing two 2,6-bis(N-alkyl-benzimidazolyl)pyridine ligands has been used to synthesize several metastable doubly threaded [3]rotaxanes in high yield (65–75% isolated) via metal templating. Macrocycle and linear thread components were synthesized and self-assembled upon addition of iron(II) ions to form the doubly threaded pseudo[3]rotaxanes that could be subsequently stoppered using azide–alkyne cycloaddition chemistry. Following demetallation with base, these doubly threaded [3]rotaxanes were fully characterized utilizing a variety of NMR spectroscopy, mass spectrometry, size-exclusion chromatography, and all-atom simulation techniques. Critical to the success of accessing a metastable [3]rotaxane with such a large macrocycle was the nature of the stopper group employed. By varying the size of the stopper group it was possible to access metastable [3]rotaxanes with stabilities in deuterated chloroform ranging from a half-life of <1 minute to ca. 6 months at room temperature potentially opening the door to interlocked materials with controllable degradation rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Patternable Mesoporous Thin Film Quantum Materials via Block Copolymer Self-Assembly: An Emergent Technology?

Recent developments in quantum materials hold promise for revolutionizing energy and information technologies. The use of soft matter self-assembly, for example, by employing block copolymers (BCPs) as structure directing or templating agents, offers facile pathways toward quantum metamaterials with highly tunable mesostructures via scalable solution processing. Here, we report the preparation of patternable mesoporous niobium carbonitride-type thin film superconductors through spin-coating of a hybrid solution containing an amphiphilic BCP swollen by niobia sol precursors and subsequent thermal processing in combination with photolithography. Spin-coated as-made BCP-niobia hybrid thin films on silicon substrates after optional photolithographic definition are heated in air to produce a porous oxide, and subsequently converted in a multistep process to carbonitrides via treatment with high temperatures in reactive gases including ammonia. Grazing incidence small-angle X-ray scattering suggests the presence of ordered mesostructures in as-made BCP-niobia films without further annealing, consistent with a distorted alternating gyroid morphology that is retained upon thermal treatments. Wide-angle X-ray scattering confirms the synthesis of phase-pure niobium carbonitride nanocrystals with rock-salt lattices within the mesoscale networks. Electrical transport measurements of unpatterned thin films show initial exponential rise in resistivity characteristic of thermal activation in granular systems down to 12.8 K, at which point resistivity drops to zero into a superconducting state. Magnetoresistance measurements determine the superconducting upper critical field to be over 16 T, demonstrating material quality on par with niobium carbonitrides obtained from traditional solid-state synthesis methods. Here. we discuss how such cost-effective and scalable solution-based quantum materials fabrication approaches may be integrated into existing microelectronics processing, promising the emergence of a technology with tremendous academic and industrial potential by combining the capabilities of soft matter self-assembly with quantum materials.

36 MATERIALS SCIENCE↗

DOE OSTI2024

A lyotropic liquid crystal-templated nanofiltration membrane with thermo- and pH-responsive 3D transport pathway

We produce controlled nanostructured membranes from cross-linking of self-assembled diacrylated poloxamers. At sufficiently high concentrations, poloxamers form lyotropic liquid crystals (LLCs), such as lamellar (L α ), cubic packing of spherical micelles, and hexagonal packing of rod-like micelles in water (H 1 ). We use the H 1 phase as a template to produce orderly packed nanofibrous membranes. The obtained membrane has a continuous 3D transport pathway and can alter its nanofiltration (NF) properties in response to changes in temperature and pH. The formulation includes Pluronic P84-diacrylate (P84DA), a thermoresponsive component that acts as both macromer and structure-directing amphiphile. P84DA facilitates changes in membrane pore size with temperature due to its thermoresponsiveness when it is in contact with water. Furthermore, the precursor contains acrylic acid (AAc) as the charged component, which upon copolymerization with P84DA, not only enables ion separation through Donnan exclusion but also imparts pH-responsive behavior for the separation of ionic species. The membrane performance is studied and compared with a commercial NF membrane (NF270). We show that the synthesized NF membrane has separation properties adjustable with temperature and pH with exceptional resistance to fouling by various solutes due to its highly hydrophilic surface. Furthermore, the membrane shows an outstanding sulfate over chloride ion selectivity, which is a requirement for salt fractionation applications. Deducted from separate experiments, the ideal chloride/sulfate selectivity for magnesium cation is about 2.38 at low ionic strengths. This study is done on a model system to show the capability of incorporating pH-responsiveness in LLC templated membranes, in which the pH-responsive range can be designed by changing the charged groups of comonomer in the formulation.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Alignment of Au nanorods along de novo designed protein nanofibers studied with automated image analysis

In this paper, we focus on exploring the directional assembly of anisotropic Au nanorods along de novo designed 1D protein nanofiber templates. Using machine learning and automated image processing, we analyze scanning electron microscopy (SEM) images to study how the attachment density and alignment fidelity are influenced by variables such as the aspect ratio of the Au nanorods, and the salt concentration of the solution. We find that the Au nanorods prefer to align parallel to the protein nanofibers. This preference decreases with increasing salt concentration, but is only weakly sensitive to the nanorod aspect ratio. While the overall specific Au nanorod attachment density to the protein fibers increases with increasing solution ionic strength, this increase is dominated primarily by non-specific binding to the substrate background, and we find that greater specific attachment (nanorods attached to the nanofiber template as compared to the substrates) occurs at the lower studied salt concentrations, with the maximum ratio of specific to non-specific binding occurring when the protein fiber solutions are prepared in 75 mM NaCl concentration.

36 MATERIALS SCIENCE↗

NASA NTRS2002

Expedite the Processing of Unpressurized Payloads to the International Space Station Using the ExPRESS Pallet

The Expedite the PRocessing of Experiments to Space Station (ExPRESS) Pallet will be used as an experiment platform for external/unpressurized payloads to be flown aboard the International Space Station (ISS). The purpose of the ExPRESS Pallet is to provide an easy access to the ISS for Scientific Investigators that require an external platform for their experiment hardware. As the name of the ExPRESS Pallet implies, the objective of the ExPRESS program is to provide a simplified integration process in a short time period (24 months) for payloads to be flown on the ISS. The ExPRESS Pallet provides unique opportunities for research across many science disciplines, including earth observation, communications, solar and deep space viewing, and long-term exposure. The ExPRESS Pallet provides access to Ram, Wake, Nadir, Zenith and Earth Limb for viewing and exposure to the space environment. The ExPRESS Pallet will provide standard physical payload interfaces, and a standard integration template. The ExPS consists of the Pallet structure, payload Adapters, a subsystem assembly that includes data controller, power distribution and conversion, and Extra Vehicular Robotics compatibility. The ExPRESS Pallet provides the capability to changeout payloads on-orbit via the ExPRESS Pallet Adapter (ExPA). The following paragraphs will describe the Services and Accommodations available to the Payload developers by the ExPRESS Pallet and a brief description of the Integration process. More detailed information on the ExPRESS Pallet can be found in the ExPRESS Pallet Payload Accommodations Handbook, SSP 52000-PAH-EPP.

Bacskay, Allen S.↗

NASA NTRS2002

Ordered nanoparticle arrays formed on engineered chaperonin protein templates

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques. Alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Some proteins, for example, have been used to form ordered two-dimensional arrays. Here, we fabricated nanoscale ordered arrays of metal and semiconductor quantum dots by binding preformed nanoparticles onto crystalline protein templates made from genetically engineered hollow double-ring structures called chaperonins. Using structural information as a guide, a thermostable recombinant chaperonin subunit was modified to assemble into chaperonins with either 3 nm or 9 nm apical pores surrounded by chemically reactive thiols. These engineered chaperonins were crystallized into two-dimensional templates up to 20 microm in diameter. The periodic solvent-exposed thiols within these crystalline templates were used to size-selectively bind and organize either gold (1.4, 5 or 10nm) or CdSe-ZnS semiconductor (4.5 nm) quantum dots into arrays. The order within the arrays was defined by the lattice of the underlying protein crystal. By combining the self-assembling properties of chaperonins with mutations guided by structural modelling, we demonstrate that quantum dots can be manipulated using modified chaperonins and organized into arrays for use in next-generation electronic and photonic devices.

Chaperonins/chemistry/ultrastructure↗

DOE OSTI2021

RNA nanotechnology to build a dodecahedral genome of single-stranded RNA virus

The quest for artificial RNA viral complexes with authentic structure while being non-replicative is on its way for the development of viral vaccines. RNA viruses contain capsid proteins that interact with the genome during morphogenesis. The sequence and properties of the protein and genome determine the structure of the virus. For example, the Pariacoto virus ssRNA genome assembles into a dodecahedron. Virus-inspired nanotechnology has progressed remarkably due to the unique structural and functional properties of viruses, which can inspire the design of novel nanomaterials. RNA is a programmable biopolymer able to self-assemble sophisticated 3D structures with rich functionalities. RNA dodecahedrons mimicking the Pariacoto virus quasi-icosahedral genome structures were constructed from both native and 2'-F modified RNA oligos. The RNA dodecahedron easily self-assembled using the stable pRNA three-way junction of bacteriophage phi29 as building blocks. The RNA dodecahedron cage was further characterized by cryo-electron microscopy and atomic force microscopy, confirming the spontaneous and homogenous formation of the RNA cage. The reported RNA dodecahedron cage will likely provide further studies on the mechanisms of interaction of the capsid protein with the viral genome while providing a template for further construction of the viral RNA scaffold to add capsid proteins for the assembly of the viral nucleocapsid as a model. Understanding the self-assembly and RNA folding of this RNA cage may offer new insights into the 3D organization of viral RNA genomes. Finally, the reported RNA cage also has the potential to be explored as a novel virus-inspired nanocarrier.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

One-Step Ligand-Exchange Method to Produce Quantum Dot–DNA Conjugates for DNA-Directed Self-Assembly

To address the current challenges in making bright, stable, and small DNA-functionalized quantum dots (QDs), we have developed a one-step ligand-exchange method to produce QD–DNA conjugates from commonly available hydrophobic QDs. We show that by systematically adjusting the reaction conditions such as ligand-to-nanoparticle molar ratio, pH, and solvent composition, stable and highly photoluminescent water-soluble QD–DNA conjugates with relatively high ligand loadings can be produced. Moreover, by site specifically binding these QD–DNA conjugates to a DNA origami template, we demonstrate that these bioconjugates have sufficient colloidal stability for DNA-directed self-assembly. Fluorescence quenching by an adjacent gold nanoparticle (AuNP) was demonstrated. Such QD–AuNP dimers may serve as biosensors with improved sensitivity and reproducibility. Furthermore, our simple method can facilitate the assembly of QDs into more complex superlattices and discrete clusters that may enable novel photophysical properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRSDate not supplied

Development of a Ground Multi-Mission Low-Cost Optical Terminal (LCOT) for Free-Space Optical Communications

Once confined to the realm of laboratory experiments and theoretical papers, space-based laser communications (lasercomm) are on the verge of achieving mainstream status. Organizations from Facebook to NASA, and missions from cubesats to Orion are employing lasercomm to achieve gigabit communication speeds at mass and power requirements lower than that of traditional radio frequency (RF) methods. Since first demonstrating free-space optical communications services with Lunar Laser Communications Demonstration (LLCD) in 2013, NASA has invested in developing optical communications technologies and capabilities to enhancing its space communications networks. Along with evolving optical space terminals, NASA is also developing lasercomm grounds stations capable of meeting the rapidly increasing data volume demands of upcoming missions, from low-earth to lunar orbits and beyond and integrating these advanced capabilities into its Near-Space and Deep Space Networks. To meet this emerging need, the Low-Cost Optical Terminal (LCOT) project at NASA’s Goddard Space Flight Center (GSFC) is designing, building and validating a prototype for a flexible, multi-mission, and economical optical ground terminal that could be used as a blueprint for a global network of optical ground stations, capable of supporting a wide variety of missions. To date a major impediment to widespread adoption of laser communication has been the lack of an existing ground network infrastructure. A mission that wishes to take advantage of laser communication not only needs to invest in an optical space terminal, but it must also finance the creation of ground terminals to receive the downlink signal. This adds significant additional cost. Missions that do decide to incur the cost of financing a network of ground terminals end up building highly specialized optical receivers that are operable as receivers for that specific mission only. Significant Non-Recurring Engineering (NRE) cost is invested to build highly specialized one-of-a-kind ground terminals that go into storage after that particular mission is over. This is not an economical approach and does nothing to grow the number of optical ground stations available to future missions. In essence each mission that wants to take advantage of the benefits of lasercom has to start from scratch to provide a ground terminal network to support it. As long as this is the case, the cost for using laser communications will be too high for most missions to consider. LCOT intends to close this gap in technology by designing and developing a standard optical ground terminal design that is flexible enough to serve as a receiver for a wide range of future missions – a ground terminal that can be quickly reconfigured to receive downlinks at different wavelengths using different signal formats. Not only does LCOT have the industry-building objectives of utilizing commercial-off-the-shelf (COTS) components to the maximum extent possible, but also spurs the commercial development of other necessary lasercomm components not currently offered by industry. Finally, LCOT will give NASA scientists and engineers a facility where they can gain real-world experience with optical communications. It will give engineers a cost-effective way to try out new concepts and processes by providing the infrastructure for such testing. In this way it is hoped LCOT will serve as a stimulus for innovation in optical communications and speed its widespread adoption by future missions. The LCOT is comprised of five subsystems: Free-Space Optical, Transceiver, Amplifier, Monitor and Control, and Observatory Infrastructure. In August 2021, the LCOT team installed a 70 cm telescope, developed by Planewave Instruments that was optimized for optical communications. Free-Space Optical subsystem comprises of the telescope and its associated hardware, including a transmitter optical assembly, wide field cameras, two optical benches, and an adaptive optics subsystem. The transmit optical assembly, a unique concept design, is a cluster of four functionally independent transmit subassemblies located on the receive telescope. In addition to receiving optical signals and directing the expanded beam with high precision to the space terminal, it also performs tracking functions. The transmit optical assembly will support operations from Low Earth Orbit (LEO) through lunar and will be used as a template for industry manufacturing. The Optical Infrastructure subsystem is responsible for providing environmentally controlled shelters for LCOT equipment and various other systems. To maintain the safety and proper functionality of the telescope, a 16 ft Astrohaven clamshell dome procured which provides all-sky coverage without the need to rotate the dome. Additionally, Atmospheric Monitoring Assembly (AMA) will be part of optical infrastructure subsystem to ensure accurate performance of the LCOT. Like existing optical ground stations, LCOT will measure standard weather station parameters, infrared all sky image of cloud cover, and cloud height. LCOT, however, adds requirements for measuring night time seeing and, in the future, daytime seeing. Unlike other optical ground terminals, the LCOT is transceiver agnostic; user transceivers may be duplex transceivers, standalone receivers, or standalone transmitters with or without acquisition beacon functionality. As such, the LCOT project accommodates testing with external customer transceivers in a flexible manor, further complimenting its intended multi-mission goals. Another unique component of LCOT is the use of a new amplifier technology – the Very Large Mode Area (VLMA) amplifiers. This new technology allows LCOT to avoid the issues faced by previous laser communications ground terminals, gives users more flexibility and modular capability, and is capable of reaching an order of magnitude higher peak power than traditional High Power Optical Amplifiers (HPOA). One drawback of the VLMA HPOA approach is that the amplified light is output into free-space. The solution developed by LCOT is an optics train that couples the output of the VLMA amplifier into a short fiber for transport to the transmit telescopes with high efficiency. Like many of the LCOT components, a set of detailed manufacturing drawings have been created for the optics train to allow any machine shop with a multi-axis Computer Numerical Control (CNC) machine to fabricate the piece parts from commonly available materials. In line with the goals of LCOT, the monitor and control functions are developed as a modular and flexible system with the ability to support future hardware or algorithm changes, minimizing disruptions. A main priority of development in the Monitor and Control Subsystem (MCS) is the safety monitor system.

laser communication↗

NASA NTRSDate not supplied

Development of a Ground Multi-mission Low Cost Optical Terminal(LCOT) for Free-Space Optical Communication

Once confined to the realm of laboratory experiments and theoretical papers, space-based laser communications (lasercomm) are on the verge of achieving mainstream status. Organizations from Facebook to NASA, and missions from cubesats to Orion are employing lasercomm to achieve gigabit communication speeds at mass and power requirements lower than that of traditional radio frequency (RF) methods. Since first demonstrating free-space optical communications services with Lunar Laser Communications Demonstration (LLCD) in 2013, NASA has invested in developing optical communications technologies and capabilities to enhancing its space communications networks. Along with evolving optical space terminals, NASA is also developing lasercomm grounds stations capable of meeting the rapidly increasing data volume demands of upcoming missions, from low-earth to lunar orbits and beyond and integrating these advanced capabilities into its Near-Space and Deep Space Networks. To meet this emerging need, the Low-Cost Optical Terminal (LCOT) project at NASA’s Goddard Space Flight Center (GSFC) is designing, building and validating a prototype for a flexible, multi-mission, and economical optical ground terminal that could be used as a blueprint for a global network of optical ground stations, capable of supporting a wide variety of missions. To date a major impediment to widespread adoption of laser communication has been the lack of an existing ground network infrastructure. A mission that wishes to take advantage of laser communication not only needs to invest in an optical space terminal, but it must also finance the creation of ground terminals to receive the downlink signal. This adds significant additional cost. Missions that do decide to incur the cost of financing a network of ground terminals end up building highly specialized optical receivers that are operable as receivers for that specific mission only. Significant Non-Recurring Engineering (NRE) cost is invested to build highly specialized one-of-a-kind ground terminals that go into storage after that particular mission is over. This is not an economical approach and does nothing to grow the number of optical ground stations available to future missions. In essence each mission that wants to take advantage of the benefits of lasercom has to start from scratch to provide a ground terminal network to support it. As long as this is the case, the cost for using laser communications will be too high for most missions to consider. LCOT intends to close this gap in technology by designing and developing a standard optical ground terminal design that is flexible enough to serve as a receiver for a wide range of future missions – a ground terminal that can be quickly reconfigured to receive downlinks at different wavelengths using different signal formats. Not only does LCOT have the industry-building objectives of utilizing commercial-off-the-shelf (COTS) components to the maximum extent possible, but also spurs the commercial development of other necessary lasercomm components not currently offered by industry. Finally, LCOT will give NASA scientists and engineers a facility where they can gain real-world experience with optical communications. It will give engineers a cost-effective way to try out new concepts and processes by providing the infrastructure for such testing. In this way it is hoped LCOT will serve as a stimulus for innovation in optical communications and speed its widespread adoption by future missions. The LCOT is comprised of five subsystems: Free-Space Optical, Transceiver, Amplifier, Monitor and Control, and Observatory Infrastructure. In August 2021, the LCOT team installed a 70 cm telescope, developed by Planewave Instruments that was optimized for optical communications. Free-Space Optical subsystem comprises of the telescope and its associated hardware, including a transmitter optical assembly, wide field cameras, two optical benches, and an adaptive optics subsystem. The transmit optical assembly, a unique concept design, is a cluster of four functionally independent transmit subassemblies located on the receive telescope. In addition to receiving optical signals and directing the expanded beam with high precision to the space terminal, it also performs tracking functions. The transmit optical assembly will support operations from Low Earth Orbit (LEO) through lunar and will be used as a template for industry manufacturing. The Optical Infrastructure subsystem is responsible for providing environmentally controlled shelters for LCOT equipment and various other systems. To maintain the safety and proper functionality of the telescope, a 16 ft Astrohaven clamshell dome procured which provides all-sky coverage without the need to rotate the dome. Additionally, Atmospheric Monitoring Assembly (AMA) will be part of optical infrastructure subsystem to ensure accurate performance of the LCOT. Like existing optical ground stations, LCOT will measure standard weather station parameters, infrared all sky image of cloud cover, and cloud height. LCOT, however, adds requirements for measuring night time seeing and, in the future, daytime seeing. Unlike other optical ground terminals, the LCOT is transceiver agnostic; user transceivers may be duplex transceivers, standalone receivers, or standalone transmitters with or without acquisition beacon functionality. As such, the LCOT project accommodates testing with external customer transceivers in a flexible manor, further complimenting its intended multi-mission goals. Another unique component of LCOT is the use of a new amplifier technology – the Very Large Mode Area (VLMA) amplifiers. This new technology allows LCOT to avoid the issues faced by previous laser communications ground terminals, gives users more flexibility and modular capability, and is capable of reaching an order of magnitude higher peak power than traditional High Power Optical Amplifiers (HPOA). One drawback of the VLMA HPOA approach is that the amplified light is output into free-space. The solution developed by LCOT is an optics train that couples the output of the VLMA amplifier into a short fiber for transport to the transmit telescopes with high efficiency. Like many of the LCOT components, a set of detailed manufacturing drawings have been created for the optics train to allow any machine shop with a multi-axis Computer Numerical Control (CNC) machine to fabricate the piece parts from commonly available materials. In line with the goals of LCOT, the monitor and control functions are developed as a modular and flexible system with the ability to support future hardware or algorithm changes, minimizing disruptions. A main priority of development in the Monitor and Control Subsystem (MCS) is the safety monitor system.

Haleh Safavi↗

DOE OSTI2020

Synthesis of Interface-Driven Tunable Bandgap Metal Oxides

Mixed bandgap and bandgap tunability in semiconductors is critical in expanding their use. Composition altera-tions through single-crystal epitaxial growth and formation of multi-layer tandem structures are often employed to achieve mixed bandgaps albeit with limited tunability. In this study, self-assembled one-dimensional coordination polymers provide a fac-ile synthon and template for graphitic C-doped mesoporous oxides, gC-β-Ga 2 O 3 or gC-In 2 O 3 via controlled oxidative ligand ablation. These materials have mixed bandgaps, and colors, depending on amount of gC present. The carbon-oxide interface leads to induced gap states, hence, a stoichiometrically tunable band structure. Structurally, a multi-scale porous network percolating throughout the material is realized. The nature of heat-treatment and top-down process allows for facile tunabil-ity and formation of mixed bandgap metal oxides through controlled carbon deposition. As a proof of concept, gC-β-Ga 2 O 3 was utilized as a photocatalyst for CO 2 reduction, which demonstrated excellent selectivity and conversion rates into CH 4 and CO.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Ultrafast dense DNA functionalization of quantum dots and rods for scalable 2D array fabrication with nanoscale precision

Scalable fabrication of two-dimensional (2D) arrays of quantum dots (QDs) and quantum rods (QRs) with nanoscale precision is required for numerous device applications. However, self-assembly–based fabrication of such arrays using DNA origami typically suffers from low yield due to inefficient QD and QR DNA functionalization. In addition, it is challenging to organize solution-assembled DNA origami arrays on 2D device substrates while maintaining their structural fidelity. Here, we reduced manufacturing time from a few days to a few minutes by preparing high-density DNA-conjugated QDs/QRs from organic solution using a dehydration and rehydration process. We used a surface-assisted large-scale assembly (SALSA) method to construct 2D origami lattices directly on solid substrates to template QD and QR 2D arrays with orientational control, with overall loading yields exceeding 90%. Our fabrication approach enables the scalable, high fidelity manufacturing of 2D addressable QDs and QRs with nanoscale orientational and spacing control for functional 2D photonic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2024

Nanoscale dynamics of Dynamin 1 helices reveals squeeze-twist deformation mode critical for membrane fission

Dynamin 1 (Dyn1) GTPase, a principal driver of membrane fission during synaptic endocytosis, self-assembles into short mechanoactive helices cleaving the necks of endocytic vesicles. While structural information about Dyn1 helix is abundant, little is known about the nanoscale dynamics of the helical scaffolding at the moment of fission, complicating mechanistic understanding of Dyn1 action. To address the role of the helix dynamics in fission, we used High-Speed Atomic Force Microscopy (HS-AFM) and fluorescence microscopy to track and compare the spatiotemporal characteristics of the helices formed by wild-type Dyn1 and its K44A mutant impaired in GTP hydrolysis on minimal lipid membrane templates. In the absence of nucleotide, membrane-bound WT Dyn1 and K44A Dyn1 self-assembled into tubular protein scaffolding of similar diameter encaging the lipid bilayer. In both cases, the GTP addition caused scaffold constriction coupled with formation of 20 to 30 nm nanogaps in the protein coverage. While both proteins reached scaffold diameters characteristic for membrane superconstriction causing fission, the fission was detected only with WT Dyn1. We associated the fission activity with the dynamic evolution of the nanogaps: K44A Dyn1 gaps were static, while WT Dyn1 gaps actively evolved via repetitive nonaxisymmetric constriction-bending deformations caused by localized GTP hydrolysis. Modeling of the deformations implicated filament twist as an additional deformation mode which combines with superconstriction to facilitate membrane fission. Our results thus show that the dynamics of the Dyn1 helical scaffold goes beyond radial constriction and involves nonaxisymmetric deformations, where filament twist emerges as a critical driver of membrane fission.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates

Utilizing the self-assembly of block copolymers with large Flory–Huggins interaction parameters (χ) for nanofabrication is a formidable challenge due to the attendant large surface energy differences between the blocks. This work reports a robust protocol for the fabrication of thin films with highly ordered cylindrical nanopore arrays via the self-assembly of an asymmetric poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) diblock copolymer blended with a P4VP homopolymer. The desired vertical domain orientation is achieved at the air–polymer interface by controlled solvent vapor annealing (SVA) using acetone, a solvent with weak selectivity for PS over P4VP, and at the substrate interface by functionalization using a hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) homopolymer brush. In contrast, the vertical cylinder orientation is unstable during acetone SVA on substrates functionalized using hydroxy-terminated poly(methyl methacrylate) (PMMA-OH). Although PMMA exhibits more balanced interfacial energies between PS and P4VP than P2VP in the dry state, it is also swollen more selectively by acetone. We hypothesize that the nearly balanced solvent swelling of the three polymers (P2VP, P4VP, and PS) stabilizes the vertical cylinder orientation, while unbalanced swelling (PMMA > P4VP and PS) does not. Here we further characterize pore formation by addition of a P4VP homopolymer and its postassembly extraction using ethanol, revealing a narrow window of pore size tunability. Notably, minimal differences in nanopore morphologies are observed for P4VP volume fractions as high as 0.1, regardless of the P4VP molar mass. However, further increasing the P4VP volume fraction results in domain reorientation or macrophase separation when its molar mass is less than or greater than the P4VP block molar mass, respectively. Using a P4VP homopolymer that is nearly equal in length to the P4VP block enables the fabrication of well-ordered arrays of vertical, through-film nanopores with high aspect ratios (>10), small periods (<23 nm), and diameters less than 10 nm.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS2004

Circular Permutation of a Chaperonin Protein: Biophysics and Application to Nanotechnology

We have designed five circular permutants of a chaperonin protein derived from the hyperthermophilic organism Sulfolobus shibatae. These permuted proteins were expressed in E. coli and are well-folded. Furthermore, all the permutants assemble into 18-mer double rings of the same form as the wild-type protein. We characterized the thermodynamics of folding for each permutant by both guanidine denaturation and differential scanning calorimetry. We also examined the assembly of chaperonin rings into higher order structures that may be used as nanoscale templates. The results show that circular permutation can be used to tune the thermodynamic properties of a protein template as well as facilitating the fusion of peptides, binding proteins or enzymes onto nanostructured templates.

Paavola, Chad↗

DOE OSTI2024

Iridium Oxide Coordinatively Unsaturated Active Sites Govern the Electrocatalytic Oxidation of Water

A special membrane electrode assembly to measure operando X-ray absorption spectra and resonant photoemission spectra of mesoporous templated iridium oxide films is used. These films are calcined to different temperatures to mediate the catalyst activity. By combining operando resonant photoemission measurements of different films with ab initio simulations these are able to unambiguously distinguish µ 2 -O (bridging oxygen) and µ 1 -O (terminal oxygen) in the near-surface regions of the catalysts. The intrinsic activity of iridium oxide scales with the formation of µ1-O (terminal oxygen) is found. Importantly, it is shown that the peroxo species do not accumulate under reaction conditions. Rather, the formation of µ 1 -O species, which are active in O-O bond formation during the OER, is the most oxidized oxygen species observed, which is consistent with an O-O rate-limiting step. Thus, the oxygen species taking part in the electrochemical oxidation of water on iridium electrodes are more involved and complex than previously stated. This result highlights the importance of employing theory together with true and complementary operando measurements capable of probing different aspects of catalysts surfaces during operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Dense Ru single-atoms integrated with sulfoacids for cellulose valorization to isosorbide

Metal-acid bifunctional catalysts are the unity of two opposites (metal-acid repelling) for cellulosic biomass valorization to isosorbide. It is challenging to improve the selectivity of metal hydrogenation catalysts and their synergism with acids for catalytic hydrolysis and dehydration to achieve substantial isosorbide. Herein, dense Ru single-atoms (10.1 wt% of Ru SAs) are anchored on sulfoacid-functionalized hollow mesoporous carbon shells, designed by assembling silica and 8-hydroxyquinoline-modified chitosan (HQ-CTS) through in situ Stöber templating strategy before pyrolysis and acid treatment. Based on X-ray absorption fine structure and computational modeling results, the structure of Ru SAs is determined as RuN 4 , which is more selective for a transitional glucose hydrogenation to sorbitol than Ru001 of Ru clusters. A lower-energy barrier of 1.21 (0.72) eV is delivered over RuN 4 (Ru001) for glucose hydrogenation (isomerization). These Ru SAs are integrated with sulfoacids (SO 3 H) but resistent against acids, rendering enhanced isosorbide yield in water as compared to Ru clusters, via a one-pot cascade reaction under harsh conditions (220 °C, 6 MPa H 2 ). The elaborately fabricated dense Ru SAs and sulfoacids, achieved by varying the addition time of HQ-CTS during the in situ Stöber templating process, improve the synergism of glucose hydrogenation with cellulose hydrolysis and sorbitol dehydration. In conclusion, this study provides a new idea for rational design of high-performance metal-acid bifunctional catalysts toward one-pot conversion of cellulose to isosorbide.

36 MATERIALS SCIENCE↗